During the operation of underground repository of high-level radioactive
waste, the highly alkaline solution generated by groundwater corroding lining
concrete will diffuse into the bentonite buffer barrier, resulting in the
degradation of barrier property. The KOH solution with different pH values was
used to simulate the alkaline solution, and a one-year contact diffusion test
at room temperature was conducted. Then, X-ray fluorescence spectroscopy (XRF),
X-ray diffraction (XRD), scanning electron microscope (SEM) and energy
dispersive spectrometry (EDS) were performed to investigate the effect of slow
diffusion on the mineralogy of bentonite. The XRF test results show that when
the pH of KOH solution was greater than 12.6, the content of silicon began to
decrease, that is, montmorillonite, quartz, cristobalite and other
Si-containing minerals in bentonite were dissolved. At the same time, the
content of K increased, indicating that the bentonite had an ion exchange
reaction with the alkaline solution, a large amount of K+ ions in
the solution entered the montmorillonite crystal layer. The XRD test results
show that the 001 peak of montmorillonite mineral started to shift to the right
at pH=12.6, the peak widths widened, and the peak intensity reduced
considerably. When the pH>13, the crystal interlayer space decreased from 1.385 3 nm (13.853 Å) to 1.221 0 nm (12.210 Å), indicating that the crystal layer
of montmorillonite was compressed. With the increase of the pH value, the
content of minerals such as montmorillonite and quartz decreased significantly,
and the contents of illite, clinoptilolite and feldspar minerals increased
slightly. The SEM test results show that part of the montmorillonite crystal
layer overlapped with the pH of the solution increasing, and then some cracks
and holes were generated. As a result, the cracks can accelerate the
dissolution of montmorillonite. In the one-year contact diffusion test, the
diffusion depth of the KOH solution with pH=13.8 exceeded 7.5 mm, and the newly
formed illite crystallites were observed on the contact surface between the alkaline solution and
the bentonite. It is confirmed that the strong alkaline solution will cause
montmorillonite dissolution and illitization.